CN107163002A - A kind of method that oxygen method prepares rubber vulcanization accelerator DM - Google Patents
A kind of method that oxygen method prepares rubber vulcanization accelerator DM Download PDFInfo
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- CN107163002A CN107163002A CN201710459206.4A CN201710459206A CN107163002A CN 107163002 A CN107163002 A CN 107163002A CN 201710459206 A CN201710459206 A CN 201710459206A CN 107163002 A CN107163002 A CN 107163002A
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- oxygen
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- vulcanization accelerator
- benzothiazole
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- 238000000034 method Methods 0.000 title claims abstract description 56
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000001301 oxygen Substances 0.000 title claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- 238000013040 rubber vulcanization Methods 0.000 title claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 16
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/78—Sulfur atoms attached to a second hetero atom to a second sulphur atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that oxygen method prepares rubber vulcanization accelerator DM.Solvent and the mercapto alcohol radical benzothiazole M of raw material 2 are added in reactor first, catalyst is then passed through into reactor, oxygen is then passed through into reactor and is reached and is reacted under certain pressure, stopping is passed through oxygen, and reaction terminates；Reaction obtains crude product 2,2 ' dithio-bis-benzothiazole DM after terminating；Gained crude product DM is filtered, filtering products therefrom is dried, product 2,2 ' dithio-bis-benzothiazole DM are obtained.Altax is prepared using the inventive method, this method is simple, low pressure, low temperature, reaction speed is fast, and cost is low, it is easy to industrialized production, and the water used of the inventive method is recyclable applies mechanically, product quality is high, high income, does not have " three wastes " discharge in building-up process.With significant economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of preparation method of thiofide, and in particular to a kind of oxygen method prepares the vulcanization of rubber
The method of altax.
Background technology
Rubber accelerator DM, its chemical name is 2, and 2 '-dibenzothiazyl disulfide is a kind of light yellow crystal, micro-
Poison, slightly odorless, bitter taste, are the extensive universal thiazole accelerators of current application, are also that a kind of very important medicine is closed
Into intermediate.Rubber accelerator DM is as the universal vulcanization accelerator of natural gum, rubber polymer and reclaimed rubber, and it is in general temperature
In the range of, rubber short vulcanization can be made, curing curve is relatively flat, DM easily disperses in sizing material, do not polluted, its sulphur in itself
Change critical-temperature higher（130℃）, increased activity when temperature is more than 140 DEG C has significant aftereffect, safe operation.Vulcanization
Glue physical and mechanical properties and ageing-resistant performance are excellent, in addition to the rubber for not being suitable for contacting with food, available for manufacture wheel
The ordinary rubber industrial goods such as tire, sebific duct, rubber overshoes, adhesive plaster, commercial Application market stability.
With the development of rubber industry, research and the production of vulcanization accelerator are increasingly valued by people.Vulcanization promotees
Enter agent and very important effect is played in Vulcanization Process of Rubber, it can greatly speed up the reaction of rubber and vulcanizing agent, improve life
Yield, while can also improve the physical and mechanical properties of vulcanization rubber, 2,2 '-dibenzothiazyl disulfide DM is current rubber work
A kind of essential primary accelerator of industry.
At present, the production technology relevant report on rubber vulcanization accelerator DM is quite a few, and main preparation methods have：1）With
Sodium hypochlorite is oxidizing M, DM is prepared by solvent of water, technical maturity, the height that product per ton about produces 10-15 tons contains
Salt waste water.2）With hydrogen peroxide oxidation M, DM is prepared as carrier with isopropanol, isopropanol, which can be followed, badly to be used, though this process
Environment-friendly type oxidant is so employed, environmental pollution reduces pressure, but hydrogen peroxide concentration is 27.5%, still produces a large amount of
Organic wastewater, adds mother liquor separation circuit, very big energy the need for mother liquor distills, and improves production cost, complex process,
It is not easy to operate.3）After M ammoniacal liquor or liquefied ammonia dissolving, ammonium salt solution filtering is obtained, catalyst is added in certain temperature and pressure
Oxygen is passed through under power or the air reaction regular hour obtains DM products, this process complex operation, ammonium salt solution needs
Filtering, it is high that whole technique needs ammonia-nitrogen content in catalyst, waste water.4）It is mixed with hydrogen peroxide and sulfuric acid at 55~65 DEG C
Compound is stablized at 6.5~7.5 as oxidant, direct oxidation Vencide salt, pH, and reaction terminates, control temperature
Separation of solid and liquid is carried out at about 30 DEG C of degree, product DM is obtained, product per ton about produces 8-10 tons of salt-containing organic wastewater.
The content of the invention
The technical problem to be solved in the present invention is：According to the development of the existing preparation method of altax, the present invention is carried
A kind of method for preparing rubber vulcanization accelerator DM for oxygen method.Accelerator DM is prepared using the inventive method, it reacts
Process safety, reaction time is shorter, temperature is low, and whole course of reaction relative energy-saving does not produce waste water, is conducive to environmental protection substantially.
In order to solve the above problems, the present invention is adopted the technical scheme that：
The present invention provides a kind of method that oxygen method prepares rubber vulcanization accelerator DM, and the preparation method comprises the following steps：
A, solvent and raw material MBT M are added in reactor first, catalyst are then passed through into reactor,
Then under conditions of temperature is 40~60 DEG C, is stirred continuously, oxygen is passed through into reactor, 0.05 is reached when reaction pressure~
Reacted 1~1.2 hour under conditions of 0.1MPa, stopping is passed through 0.2~0.6h of oxygen, stop being passed through in oxygen process at this and react
Kettle pressure is constant, then reaction reaches terminal；Reaction obtains crude product 2,2 '-dithio-bis-benzothiazole DM after terminating；
The solvent and raw material MBT M mass ratio are 1~15:1, the catalyst with raw material 2- mercapto alcohol
Base benzothiazole M mass ratio is 1:8000~10000；
B, crude product DM obtained by step a filtered, dried to filtering products therefrom, obtain product 2,2 '-two thio two
Benzothiazole DM.
The method that rubber vulcanization accelerator DM is prepared according to above-mentioned oxygen method, solvent described in step a be water, ethanol,
Methanol, isopropanol, benzene or toluene.
The method for preparing rubber vulcanization accelerator DM according to above-mentioned oxygen method, catalyst described in step a is NO and NO2
Mixture, mixing mol ratio therebetween is 1:2~6.
The method that rubber vulcanization accelerator DM is prepared according to above-mentioned oxygen method, stirring when being stirred continuously described in step a
Speed is mixed for 300~600r/min.
The method that rubber vulcanization accelerator DM is prepared according to above-mentioned oxygen method, drying described in step b be using 140~
150 DEG C of nitrogen is dried.
NO and NO are employed in technical solution of the present invention2Mixture be used as catalyst carry out prepare 2,2 '-two thio two
Benzothiazole DM, its reaction mechanism is as follows：
2RSH + NO2 →RSSR + NO +H2O (1)
2NO+O2→2NO2 (2)
Overall reaction equation is as follows：
4RSH + O2→2RSSR + 2H2O (3)
In addition, the reaction mechanism design sketch that the present invention reacts refers to accompanying drawing 6.
The positive beneficial effect of the present invention：
1st, using synthesizing rubber vulcanization accelerator DM by oxygen oxidization of the present invention, wherein the catalyst used is NO and NO2It is mixed
Compound；The inventive method is simple, low pressure, low temperature, and reaction speed is fast, and cost is low, it is easy to industrialized production, and the inventive method is used
To water it is recyclable apply mechanically, product quality is high, high income, does not have " three wastes " discharge in building-up process.With significant economic effect
Benefit and social benefit.
2nd, the inventive method understands that the present invention has advantages below with existing DM preparation technologies contrast：
1）The present invention is nearly free from waste water during preparing altax（Mother liquor can be recycled completely）, waste gas and useless
Liquid；
2）The present invention prepares DM course of reaction safety；
3）The present invention prepares DM, and its yield is significantly improved, and high income is up to more than 96%, and products obtained therefrom purity is higher, and purity reaches
More than 97%；And preparation method of the present invention solves the problem of DM product heap density is small.
Brief description of the drawings：
The liquid chromatogram of the products obtained therefrom of Fig. 1 embodiment of the present invention 1；
The liquid chromatogram of the products obtained therefrom of Fig. 2 embodiment of the present invention 2；
The liquid chromatogram of the products obtained therefrom of Fig. 3 embodiment of the present invention 3；
The liquid chromatogram of the products obtained therefrom of Fig. 4 embodiment of the present invention 4；
The liquid chromatogram of the products obtained therefrom of Fig. 5 embodiment of the present invention 5；
The reaction mechanism design sketch that Fig. 6 present invention reacts.
Embodiment：
The present invention is expanded on further with reference to embodiments, but is not intended to limit present disclosure.
Embodiment 1：
The method that oxygen method of the present invention prepares rubber vulcanization accelerator DM, the detailed step of the preparation method is as follows：
A, water 300g and raw material MBT 30g are added in 1000mL stainless steel cauldrons first, then to anti-
Answer and catalyst 0.0035g is passed through in kettle（Catalyst is NO and NO2Mixture, mixing mol ratio therebetween is 1:3）, connect
Under conditions of temperature is 40 DEG C, is stirred continuously（Mixing speed is 300r/min）, oxygen is passed through into reactor, works as reaction
Pressure reacts 1 hour under conditions of reaching 0.05~0.1MPa, and stopping is passed through oxygen 0.2h, and reaction terminates；Obtain crude product 2,2 '-
Dithio-bis-benzothiazole DM；
B, crude product DM obtained by step a filtered, dried to filtering products therefrom（Dried using 140 DEG C of nitrogen
It is dry）, obtain product 2,2 '-dithio-bis-benzothiazole DM.
By statistical calculation：The present embodiment reaction yield is 96.7%, and product purity is 96.2%, and product is in pale solid.
Embodiment 2：
The method that oxygen method of the present invention prepares rubber vulcanization accelerator DM, the detailed step of the preparation method is as follows：
A, water 300g and raw material MBT 30g are added in 500mL stainless steel cauldrons first, then to reaction
Catalyst 0.0037g is passed through in kettle（Catalyst is NO and NO2Mixture, mixing mol ratio therebetween is 1:2）, then
Under conditions of temperature is 50 DEG C, is stirred continuously（Mixing speed is 400r/min）, oxygen is passed through into reactor, works as reaction pressure
Power is reacted 1 hour under conditions of reaching 0.05~0.1MPa, and stopping is passed through oxygen 0.3h, and reaction terminates；Obtain crude product 2,2 '-two
Thio bisbenzothiazole DM；
B, crude product DM obtained by step a filtered, dried to filtering products therefrom（Dried using 140 DEG C of nitrogen
It is dry）, obtain product 2,2 '-dithio-bis-benzothiazole DM.
By statistical calculation：The present embodiment reaction yield is 96.6%, and product purity is 96.8%, and product is in pale solid.
Embodiment 3：
The method that oxygen method of the present invention prepares rubber vulcanization accelerator DM, the detailed step of the preparation method is as follows：
A, water 300g and raw material MBT 30g are added in 500mL stainless steel cauldrons first, then to reaction
Catalyst 0.003g is passed through in kettle（Catalyst is NO and NO2Mixture, mixing mol ratio therebetween is 1:3）, then
Under conditions of temperature is 40 DEG C, is stirred continuously（Mixing speed is 400r/min）, oxygen is passed through into reactor, works as reaction pressure
Power is reacted 1 hour under conditions of reaching 0.05~0.1MPa, and stopping is passed through oxygen 0.3h, and reaction terminates；Obtain crude product 2,2 '-two
Thio bisbenzothiazole DM；
B, crude product DM obtained by step a filtered, dried to filtering products therefrom（Dried using 140 DEG C of nitrogen
It is dry）, obtain product 2,2 '-dithio-bis-benzothiazole DM.
By statistical calculation：The present embodiment reaction yield is 96.3%, and product purity is 97.2%, and product is in pale solid.
Embodiment 4：
The method that oxygen method of the present invention prepares rubber vulcanization accelerator DM, the detailed step of the preparation method is as follows：
A, water 300g and raw material MBT 30g are added in 500mL stainless steel cauldrons first, then to reaction
Catalyst 0.0032g is passed through in kettle（Catalyst is NO and NO2Mixture, mixing mol ratio therebetween is 1:5）, then
Under conditions of temperature is 50 DEG C, is stirred continuously（Mixing speed is 300r/min）, oxygen is passed through into reactor, works as reaction pressure
Power is reacted 1 hour under conditions of reaching 0.05~0.1MPa, and stopping is passed through oxygen 0.6h, and reaction terminates；Obtain crude product 2,2 '-two
Thio bisbenzothiazole DM；
B, crude product DM obtained by step a filtered, dried to filtering products therefrom（Dried using 140 DEG C of nitrogen
It is dry）, obtain product 2,2 '-dithio-bis-benzothiazole DM.
By statistical calculation：The present embodiment reaction yield is 96.3%, and product purity is 97.4%, and product is in pale solid.
Embodiment 5：
The method that oxygen method of the present invention prepares rubber vulcanization accelerator DM, the detailed step of the preparation method is as follows：
A, water 300g and raw material MBT 30g are added in 1000mL stainless steel cauldrons first, then to anti-
Answer and catalyst 0.0036g is passed through in kettle（Catalyst is NO and NO2Mixture, mixing mol ratio therebetween is 1:4）, connect
Under conditions of temperature is 50 DEG C, is stirred continuously（Mixing speed is 600r/min）, oxygen is passed through into reactor, works as reaction
Pressure reacts 1 hour under conditions of reaching 0.05~0.1MPa, and stopping is passed through oxygen 0.2h, and reaction terminates；Obtain crude product 2,2 '-
Dithio-bis-benzothiazole DM；
B, crude product DM obtained by step a filtered, dried to filtering products therefrom（Dried using 140 DEG C of nitrogen
It is dry）, obtain product 2,2 '-dithio-bis-benzothiazole DM.
By statistical calculation：The present embodiment reaction yield is 96.4%, and product purity is 97.1%, and product is in pale solid.
Claims (5)
1. a kind of method that oxygen method prepares rubber vulcanization accelerator DM, it is characterised in that the preparation method includes following step
Suddenly：
A, solvent and raw material MBT M are added in reactor first, catalyst are then passed through into reactor,
Then under conditions of temperature is 40~60 DEG C, is stirred continuously, oxygen is passed through into reactor, 0.05 is reached when reaction pressure~
Reacted 1~1.2 hour under conditions of 0.1MPa, stopping is passed through 0.2~0.6h of oxygen, stop being passed through in oxygen process at this and react
Kettle pressure is constant, then reaction reaches terminal；Reaction obtains crude product 2,2 '-dithio-bis-benzothiazole DM after terminating；
The solvent and raw material MBT M mass ratio are 1~15:1, the catalyst with raw material 2- mercapto alcohol
Base benzothiazole M mass ratio is 1:8000~10000；
B, crude product DM obtained by step a filtered, dried to filtering products therefrom, obtain product 2,2 '-two thio two
Benzothiazole DM.
2. the method that oxygen method according to claim 1 prepares rubber vulcanization accelerator DM, it is characterised in that：In step a
The solvent is water, ethanol, methanol, isopropanol, benzene or toluene.
3. the method that oxygen method according to claim 1 prepares rubber vulcanization accelerator DM, it is characterised in that：In step a
The catalyst is NO and NO2Mixture, mixing mol ratio therebetween is 1:2~6.
4. the method that oxygen method according to claim 1 prepares rubber vulcanization accelerator DM, it is characterised in that：In step a
Mixing speed when being stirred continuously is 300~600r/min.
5. the method that oxygen method according to claim 1 prepares rubber vulcanization accelerator DM, it is characterised in that：In step b
The drying is dried using 140~150 DEG C of nitrogen.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727296A (en) * | 2017-10-23 | 2018-11-02 | 内蒙古科迈化工有限公司 | A kind of dioxygen oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide |
| CN110330466A (en) * | 2019-07-25 | 2019-10-15 | 山东金城医药化工有限公司 | The method of curing di-mercaptobenzothiazolby is recycled from cephalo active ester production mother liquor |
| CN110776478A (en) * | 2019-11-11 | 2020-02-11 | 山东阳谷华泰化工股份有限公司 | Low-temperature continuous synthesis method of rubber vulcanization accelerator NS |
-
2017
- 2017-06-16 CN CN201710459206.4A patent/CN107163002B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 单鑫: "硫化促进剂DM工业合成机理探讨", 《工业催化》 * |
| 孟冬: "药用二硫化二苯并噻唑DM工业生产关键技术", 《中国优秀硕士学位论文工程科技1辑 青岛科技大学硕士学位论文》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727296A (en) * | 2017-10-23 | 2018-11-02 | 内蒙古科迈化工有限公司 | A kind of dioxygen oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide |
| CN110330466A (en) * | 2019-07-25 | 2019-10-15 | 山东金城医药化工有限公司 | The method of curing di-mercaptobenzothiazolby is recycled from cephalo active ester production mother liquor |
| CN110776478A (en) * | 2019-11-11 | 2020-02-11 | 山东阳谷华泰化工股份有限公司 | Low-temperature continuous synthesis method of rubber vulcanization accelerator NS |
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